A computational fluid dynamics (CFD) model is developed to predict gas dynamic behavior in a high-velocity oxy-fuel (HVOF) thermal spray gun in which premixed oxygen and propylene are burnt in a 12 mm combustion chamber linked to a parallel-sided nozzle. The CFD analysis is applied to investigate axisymmetric, steady-state, turbulent, compressible, and chemically combusting flow both within the gun and in a free jet region between the gun and the substrate to be coated. The combustion of oxygen and propylene is modeled using a single-step, finite-rate chemistry model that also allows for dissociation of the reaction products. Results are presented to show the effect of (1) fuel-to-oxygen gas ratio and (2) total gas flow rate on the gas dynamic behavior. Along the centerline, the maximum temperature reached is insensitive to the gas ratio but depends on the total flow. However, the value attained (
Shen DK, Gu S, Bridgwater AV (2010) The thermal performance of the polysaccharides extracted from hardwood: Cellulose and hemicelluloses, Carbohydrate Polymers 82 (1, 2 August 2010) pp. 39-45 Elsevier B.V.
The pyrolytic behaviour of individual component in biomass needs to be understood to gain insight into the mechanism of biomass pyrolysis. A comparative study on the pyrolysis of cellulose (hexose-based polysaccharides) and hemicallulose (pentose-based polysaccharides) is performed by two sets of experiments including TG analysis and Py-GC?MS/FTIR. The samples of these two polysaccharide components are thermally decomposed in TGA at the heating rate of 5 and 60 K/min to demonstrate the different characteristics of mass loss stage(s) between them. The yield of pyrolytic products is examined by a fluidized-bed fast pyrolysis unit. The experiment confirms that cellulose mainly contributes to bio-oil production (reaching the maximum of 72% at 580 °C), while hemicellulose works as an important precursor for the char production (
High velocity oxygen?fuel (HVOF) thermal spraying is a relatively new technology compared to other protective coating methods. Powders sprayed by liquid fuel HVOF guns are able to achieve high impact velocities without overheating, which results in superior coatings. A computational fluid dynamic (CFD) model is developed to investigate propane combustion in the process of HVOF thermal spraying. The numerical methods are described for correct representation of various thermal?physical phenomena such as flame propagation, turbulent mixing and flow acceleration. The principal advantages and shortcomings of various models are discussed.
Das S, Bhattacharya A, Haldar S, Ganguly A, Gu S, Ting YP, Chatterjee PK (2015) Optimization of enzymatic saccharification of water hyacinth biomass for bio-ethanol: Comparison between artificial neural network and response surface methodology, Sustainable Materials and Technologies 3 (April 2015) pp. 17-28 Elsevier B.V.
Response surface methodology (RSM) is commonly used for optimising process parameters affecting enzymatic hydrolysis. However, artificial neural network?genetic algorithm hybrid model can also serve as an effective option, primarily for non-linear polynomial systems. The present study compares these approaches for enzymatic hydrolysis of water hyacinth biomass to maximise total reducing sugar (TRS) for bio-ethanol production. Maximum TRS (0.5672 g/g) was obtained using 9.92 (% w/w) substrate concentrations, 49.56 U/g cellulase concentrations, 280.33 U/g xylanase concentrations and 0.13 (% w/w) surfactant concentrations. The average % error for artificial neural networking (ANN) and RSM were 3.08 and 4.82 and the prediction percentage errors in optimum output are 0.95 and 1.41, respectively, which showed the supremacy of ANN in illustrating the non-linear behaviour of the system. Fermentation of the hydrolysate yielded a maximum ethanol concentration of 10.44 g/l using Pichia stipitis, followed by 8.24 and 6.76 g/l for Candida shehatae and Saccharomyces cerevisiae.
Armstrong LM, Luo KH, Gu S (2010) Two-dimensional and Three-dimensional Computational Studies of Hydrodynamics in the Transition from Bubbling to Circulating Fluidised Bed, Chemical Engineering Journal 160 (1, 15 May 2010) pp. 239-248 Elsevier B.V.
This paper applies two-fluid modelling (TFM) to a two-dimensional and three-dimensional circulating fluidised bed (CFB). An energy minimisation multiscale (EMMS) based drag model is compared with a classical drag model, namely the Gidaspow model in the light of experimental data from the CFB. The axial particle velocities and the radial volume fraction at different heights are considered. The specularity coefficient responsible for the tangential solid velocities at the walls is varied to study the effect on the downflow of particles at the wall. The work is further extended to explore the effects of velocity variation on the flow distribution showing the transition from a bubbling to a fast fluidising regime. Furthermore, the diameters of the bubbles observed within the bubbling regime are compared with the Davidson?s bubble diameter model for a range of particle diameters. Varying the specularity coefficient showed that a free slip boundary condition underpredicted the downflow of particles at the wall and to add slight roughness to the wall gave a closer representation. The predictions for the 2D and 3D CFB axial velocities were in good agreement with the experimental data but the 2D results slightly overpredicted the core velocity. The transition from a bubbling to a fast fluidising regime as expected occurred once the inlet velocity exceeded the terminal velocity. The equivalent bubble diameter from the simulations agreed well with the calculated bubble diameter from the model.
Papadikis K, Gu S, Fivga A, Bridgwater AV (2010) Numerical comparison of the drag models of granular flows applied to the fast pyrolysis of biomass, Energy and Fuels 24 (3) pp. 2133-2145 ACS Publications
The paper presents a comparison between the different drag models for granular flows developed in the
literature and the effect of each one of them on the fast pyrolysis of wood. The process takes place on an
100 g/h lab scale bubbling fluidized bed reactor located at Aston University. FLUENT 6.3 is used as the
modeling framework of the fluidized bed hydrodynamics, while the fast pyrolysis of the discrete wood
particles is incorporated as an external user defined function (UDF) hooked to FLUENT?s main code
structure. Three different drag models for granular flows are compared, namely the Gidaspow, Syamlal
O?Brien, and Wen-Yu, already incorporated in FLUENT?s main code, and their impact on particle
trajectory, heat transfer, degradation rate, product yields, and char residence time is quantified. The
Eulerian approach is used to model the bubbling behavior of the sand, which is treated as a continuum.
Biomass reaction kinetics is modeled according to the literature using a two-stage, semiglobal model that
takes into account secondary reactions.
Shen DK, Gu S (2009) The mechanism for thermal decomposition of cellulose and its main products, Bioresource Technology 100 (24, December 2009) pp. 6496-6504 ScienceDirect
Experiment is performed to investigate the mechanism of the cellulose pyrolysis and the formation of the main products. The evolution of the gaseous products is examined by the 3-D FTIR spectrogram at the heating rate of 5?60 K/min. A pyrolysis unit, composed of fluidized bed reactor, carbon filter, vapour condensing system and gas storage, is employed to investigate the products of the cellulose pyrolysis under different temperatures (430?730 °C) and residence time (0.44?1.32 s). The composition in the bio-oil is characterized by GC?MS while the gases sample is analyzed by GC. The effects of temperature and residence time on the main products in bio-oil (LG, 5-HMF, FF, HAA, HA and PA) are examined thoroughly. Furthermore the possible routes for the formation of the products are developed from the direct conversion of cellulose molecules and the secondary reactions of the fragments. It is found that the formation of CO is enhanced with elevated temperature and residence time, while slight change is observed for the yield of CO2.
Tabbara H, Gu S, McCartney DG (2011) Computational modelling of titanium particles in warm spray, Computers & Fluids 44 (1 (May 2011)) pp. 358-368 Elsevier B.V.
A warm spray system has been computationally investigated by introducing a centrally located mixing chamber into a HVOF thermal spray gun. The effects of injecting a cooling gas on the gas and particle dynamics are examined. The gas phase model incorporates liquid fuel droplets which heat, evaporate and then exothermically combust with oxygen within the combustion chamber producing a realistic compressible, supersonic and turbulent jet. The titanium powder is tracked using the Lagrangian approach including particle heating, melting and solidification. The results present an insight into the complex interrelations between the gas and particle phases, and highlight the advantage of warm spray, especially for the deposition of oxygen sensitive materials such as titanium. This work also demonstrates the effectiveness of a computational approach in aiding the development of thermal spray devices.
In this study, the three-dimensional steady-state non-transferred plasma arc was investigated using computational fluid dynamics (CFD) with user defined functions (UDFs). A two-equation current density profile was developed to simulate the complex plasma flow inside the torch. The effect of the deviation distance (distance between the cathode tip center and the current density profile center) on the plasma flow features was systematically investigated for the first time. It is found that the temperature and velocity inside the plasma column reduce as the deviation distance increases, but the temperature near the arc-root attachment shows an increasing trend. Besides, it is also found that the arc length decreases with increasing the deviation distance.
Armstrong LM, Gu S, Luo KH (2013) Dry pressure drop prediction within Montz-Pak B1-250.45 packing with varied inclination angles and geometries, Industrial and Engineering Chemistry Research 52 (11) pp. 4372-4378
Structured packings are used to increase the surface area and promote gas?liquid contact in many chemical processes, including carbon capture. Computational fluid dynamics and performance prediction methods have the ability to aid the optimization of the structured packing designs to aid the heat and mass transfer while minimizing the pressure drop. The present work introduces pressure drop correlations that determine frictional pressure loss between Montz-Pak B1-250.45 structured packing sheets based on the inclination angle and channel geometry of the sheets. CFD simulations are carried out on the packing and are validated against published experimental data.
Kishore N, Gu S (2010) Wall Effects on Flow and Drag Phenomena of Spheroid Particles at Moderate Reynolds Numbers, Industrial and Engineering Chemistry Research 49 (19 (2010)) pp. 9486-9495 ACS Publications
Two dimensional steady Newtonian flow past oblate and prolate spheroid particles confined in cylindrical tubes of different diameters has been numerically investigated. The flow and drag phenomena of confined spheroid particles are governed by the equations of continuity and conservation of momentum. These equations along with appropriate boundary conditions have been solved using commercial software based on computational fluid dynamics. Extensive new results were obtained on individual and total drag coefficients of spheroid particles, along with streamline contours, distributions of pressure coefficients, and vorticity magnitudes on the surface of spheroid particles as functions of the Reynolds number (Re), the aspect ratio (e), and the wall factor (») over the following range of conditions: 1 d Re d 200, 0.25 d e d 2.5, and 2 d » d 30. For all values of the aspect ratio, as values of the Reynolds numbers and/or the wall factor increase, the length of recirculation wake increases. For fixed values of the aspect ratio and the Reynolds number, the increase in the value of the wall factor decrease both individual and the total drag coefficients. On the whole, regardless of the value of the aspect ratio, the wall effect was found to gradually diminish with the increasing Reynolds number and/or the wall factor. Finally, on the basis of the present numerical results a simple correlation has been proposed for the total drag coefficient of confined spheroid particles which can be used in new applications.
Singh J, Gu S (2010) Biomass Conversion to Energy in India ? A Critique, Renewable & Sustainable Energy Reviews 14 (5, June 2010) pp. 1367-1378 Elsevier B.V.
This paper critically discusses the scope, potential and implementation of biomass conversion to energy in Indian scenario. The feasibility as well as suitability of the various categories of biomass to energy in India has been discussed. Brief descriptions of potential conversion routes have been included, with their possible and existing scope of implementation in Indian context. As far as possible, the most recent statistical data have been reported from the available sources. The figures reported have been updated as on March 2009, in most of the cases. The discussion reveals that a large potential exists for the biomass feed-stocks from the various kinds of waste biomass. The gasification as well as anaerobic digestion processes seem to be most attractive in Indian scenario.
Shen DK, Gu S, Luo KH, Wang SR, Fang MX (2010) The pyrolytic degradation of wood-derived lignin from pulping process, Bioresource Technology 101 (15, August 2010) pp. 6136-6146 Elsevier B.V.
Lignin is a key component in the biomass with a complex polymeric structure of the phenyl-C3 alkyl units. The kraft lignin from the wood pulping process is tested in TG-FTIR and Py-GC-MS. The samples are pyrolyzed in TGA coupled with FTIR from 30 to 900 °C at the heating rate of 20 and 40 K/min. The evolution of phenolic compounds in the initial pyrolysis stage of lignin is determined by FTIR, while the second stage is mainly attributed to the production of the low molecular weight species. A bench-scale fast pyrolysis unit is employed to investigate the effect of temperature on the product yield and composition. It is found that the guaiacol-type and syringol-type compounds as the primary products of lignin pyrolysis are predominant in bio-oil, acting as the significant precursors for the formation of the derivatives such as the phenol-, cresol- and catechol-types. A series of free-radical chain-reactions, concerning the cracking of different side-chain structures and the methoxy groups on aromatic ring, are proposed to demonstrate the formation pathways for the typical compounds in bio-oil by closely relating lignin structure to the pyrolytic mechanisms. The methoxy group (?OCH3) is suggested to work as an important source for the formation of the small volatile species (CO, CO2 and CH4) through the relevant free radical coupling reactions.
Guo Z, Yin S, Liao H, Gu S (2014) Three-dimensional simulation of an argon?hydrogen DC non-transferred arc plasma torch, International Journal of Heat and Mass Transfer 80 (January 2015) pp. 644-652 Elsevier
Simulations of a DC non-transferred arc plasma torch operating with argon?hydrogen have been performed by using a three-dimensional model. An artificially high electrical conductivity layer is employed to allow the current passing through the low temperature region near the anode wall. A new way by using two equations to describe the current density distribution is developed. Besides, a new method for determining the location of the arc-root attachment is proposed, in which the minimum total heat transfer rate through the anode wall is considered as the criterion for the lowest energy loss. Based on this criterion, the real arc core radius and length are predicted. Moreover, the influences of arc current and mass flow rate on the plasma arc characteristics are also investigated. The results obtained show that the location of the arc-root attachment predicted by the minimum total heat transfer rate principle is in good agreement with the previous work and the experimental data. Additionally, it is found that arc length can be reduced by increasing current or decreasing flow rate. Also, higher current and flow rate lead to higher temperature and velocity inside the plasma torch.
Kiran Kumar Palla VS, Papadikis K, Gu S (2015) A numerical model for the fractional condensation of pyrolysis vapours, Biomass and Bioenergy 74 (March 2015) pp. 180-192 Elsevier B.V.
Experimentation on the fast pyrolysis process has been primarily focused on the pyrolysis reactor itself, with less emphasis given to the liquid collection system (LCS). More importantly, the physics behind the vapour condensation process in LCSs has not been thoroughly researched mainly due to the complexity of the phenomena involved. The present work focusses on providing detailed information of the condensation process within the LCS, which consists of a water cooled indirect contact condenser. In an effort to understand the mass transfer phenomena within the LCS, a numerical simulation was performed using the Eulerian approach. A multiphase multi-component model, with the condensable vapours and non-condensable gases as the gaseous phase and the condensed bio-oil as the liquid phase, has been created. Species transport modelling has been used to capture the detailed physical phenomena of 11 major compounds present in the pyrolysis vapours. The development of the condensation model relies on the saturation pressures of the individual compounds based on the corresponding states correlations and assuming that the pyrolysis vapours form an ideal mixture. After the numerical analysis, results showed that different species condense at different times and at different rates. In this simulation, acidic components like acetic acid and formic acids were not condensed as it was also evident in experimental works, were the pH value of the condensed oil is higher than subsequent stages. In the future, the current computational model can provide significant aid in the design and optimization of different types of LCSs.
Zeoli N, Gu S (2007) Computational simulation of metal droplet break-up, cooling and solidification during gas atomisation, Computational Materials Science 43 (2, August 2008) pp. 268-278 ScienceDirect
In an atomisation process for powder production, metal droplets go through undercooling, recalescence, peritectic and segregated solidification before fully solidified. The cooling process is further complicated by droplet break-up during the atomisation. This paper describes a numerical model which combines both cooling and break-up in a single computation. The dynamic history of droplets is solved as discrete phase in an Eulerian gas flow. The coupling between droplet and gas flows are two-way, in which the heat and momentum exchanges affecting the gas flow are treated as source/sink terms in the fluid equations. The droplet models were employed a gas atomisation process for metal powder production and good agreement is achieved with the results in open literature. The model results further confirm that thermal history of particles is strongly dependent on initial droplet size. Large droplets will not go through undercooling while small droplets have identifiable stages of undercooling, unclearation and recalescence. The predictions demonstrate that droplets have very similar profiles during gas atomisation and the major factor influencing the atomisation and solidification process of droplets are in-flight distance.
Shemfe MB, Fidalgo B, Gu S (2015) Heat integration for bio-oil hydroprocessing coupled with aqueous phase steam reforming, CHEMICAL ENGINEERING RESEARCH & DESIGN 107 pp. 73-80 INST CHEMICAL ENGINEERS
Kishore N, Gu S (2011) Effect of Blockage on Heat Transfer Phenomena of Spheroid Particles at Moderate Reynolds and Prandtl Numbers, Chemical Engineering Technology 34 (9, September 2011) pp. 1551-1558
Effects of the confining wall or blockage on the heat transfer phenomena of spheroid particles were numerically investigated. The heated spheroid particles were maintained at constant temperature and allowed to sediment in cylindrical tubes filled with Newtonian liquids. In this flow configuration, the heat transfer took place from the heated spheroid particles to the surrounding Newtonian liquid. The governing conservation equations of the mass, momentum, and energy together with appropriate boundary conditions were numerically solved using commercial software based on computational fluid dynamics. A simple correlation for the average Nusselt number of the confined spheroid particles was developed which can be applied in new applications.
Zeoli N, Gu S (2006) Numerical modelling of droplet break-up for gas atomisation, Computational Materials Science 38 (2, December 2006) pp. 282-292 ScienceDirect
High-pressure gas atomisation (HPGA) technology has been widely employed as an effective method to produce fine spherical metal powders. The physics of gas atomisation is dominated by rapid momentum and heat transfer between the gas and melt phases, and further complicated by break-up and solidification. A numerical model is developed to simulate the critical droplet break-up during the atomisation. By integration of the droplet break-up model with the flow field generated high-pressure gas nozzle, this numerical model is able to provide quantitative assessment for atomisation process. To verify the model performance, the melt stream is initialized to large droplets varying from 1 to 5 mm diameters and injected into the gas flow field for further fragmentation and the break-up dynamics are described in details according to the droplet input parameters.
The fluid?particle interaction inside a 150 g/h fluidised bed reactor is modelled. The biomass particle is injected into the fluidised bed and the heat, momentum and mass transport from the fluidising gas and fluidised sand is modelled. The Eulerian approach is used to model the bubbling behaviour of the sand, which is treated as a continuum. Heat transfer from the bubbling bed to the discrete biomass particle, as well as biomass reaction kinetics are modelled according to the literature. The particle motion inside the reactor is computed using drag laws, dependent on the local volume fraction of each phase. FLUENT 6.2 has been used as the modelling framework of the simulations with the whole pyrolysis model incorporated in the form of user-defined function (UDF). The study completes the fast pyrolysis modelling in bubbling fluidised bed reactors.
Zeoli N, Tabbara H, Gu S (2011) CFD modelling of primary breakup during metal powder atomization, Chemical Engineering Science 66 (24 (15 December 2011)) pp. 6498-6504 Elsevier B.V.
Powder metals are the basis of powder metallurgy with a large variety of applications, including sintering and thermal spray coatings. The Gas atomization process has been widely employed as an effective method to produce fine spherical metal powders. New applications and emerging surface technologies demand high quality powders with a very narrow particle size distribution. A computational fluid dynamics (CFD) approach is developed to examine complex fluids during atomization from different nozzle designs, using the volume of fluid (VOF) method and the Reynolds Stress Model (RSM). The modeling results show that the swirling gas atomizer is not beneficial to the atomization process while the inner-jet atomizer can improve the powder generation processing.
Gu S, Kamnis S (2009) Numerical Modelling of In-Flight Particle Dynamics of Non-Spherical Powder, Surface and Coatings Technology 203 (22, 15 August 2009) pp. 3485-3490 Elsevier B.V.
High velocity oxygen fuel (HVOF) is an important thermal spraying technology in depositing high quality coatings. Its ability to produce high particle velocities and relatively low particle temperatures is its most salient feature. Several computational fluid dynamic (CFD) models have been developed to study the in-flight particle behavior during thermal spraying. These models are limited to spherical particles, which are only appropriate for modelling gas atomised powders. On the other hand, hardmetal powders such as WC-Co are created using high energy ball milling and are not normally spherical. To examine the effect of particle morphology on particle dynamics, mathematical models are developed in the present paper to predict the in-flight particle behavior in a liquid fuelled HVOF thermal spray gun. The particle transport equations are coupled with the three-dimensional, chemically reacting, turbulent gas flow, and solved in a Lagrangian manner. The melting and solidification within the particles as a result of heat exchange with the surrounding gas flow are solved numerically. The results demonstrate that non-spherical particles gain more momentum and less heat during the HVOF process than spherical particles. Non-spherical particles are also predicted to stay closer to the center of the gas jet than spherical particles.
An Eulerian-Eulerian computational fluid dynamics (CFD) model of the gasification processes in a coal bubbling fluidized bed (BFB) is presented based on the experimental setup taken from the literature. The base model is modified to account for different parameter changes in the model setup. The exiting gas compositions for the base model have been averaged over time and validated with experimental data and compared to the exiting results for the different parameter models. An extensive study is also carried out which considers the variation of different parameters such as bed temperatures, bed height, bed material, heat transfer coefficients, and devolatilization models influenced the gasification processes in different ways. Such an extensive parametric study has yet to be carried out for an Eulerian-Eulerian coal gasification model.
Shen DK, Liu N, Dong C, Xiao R, Gu S (2015) Catalytic solvolysis of lignin with the modified HUSYs in formic acid assisted by microwave heating, Chemical Engineering Journal 270 (15 June 2015) pp. 641-647 Elsevier B.V.
Microwave-assisted catalytic solvolysis of lignin in formic acid was studied concerning the addition of HUSY catalysts modified by oxalic acid. Characteristics of the modified catalysts were examined by XRD, NH3-TPD and BET. The highest yield of liquid product was achieved as 88.28 wt% (aromatic monomer fraction as bio-oil 1 of 15.36% and oligomer fraction as bio-oil 2 of 67.52%) with the addition of HUSY modified by 0.2 mol/L oxalic acid (HUSY-0.2 M). The production of aromatic monomers in bio-oil 1 identified by GC/MS was enhanced with the addition of HUSY catalysts regardless of acidic treatment, and achieved the maximum value for HUSY-0.2 M experiment. Aromatic oligomers with molecular weight of 328, 342, 358, 378, 394, 424 and 454 were characterized by Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry (MALDI-TOF MS) analysis. Formation of almost all identified oligomers was promoted with catalytic experiments with HUSYs except that of 328, extent of which is significantly determined by the pore size, Si/Al ratio and acidic site distribution of the modified catalysts.
Gasification is the thermochemical conversion of solid fuel into the gas which contains mainly hydrogen, carbon monoxide, carbon dioxide, methane and nitrogen. In gasification, fluidized bed technology is widely used due to its various advantageous features which include high heat transfer, uniform and controllable temperature and favorable gas?solid contacting. Modeling and simulation of fluidized bed gasification is useful for optimizing the gasifier design and operation with minimal temporal and financial cost. The present work investigates the different modeling approaches applied to the fluidized bed gasification systems. These models are broadly classified as the equilibrium model and the rate based or kinetic model. On the other hand, depending on the description of the hydrodynamic of the bed, fluidized bed models may also be classified as the two-phase flow model, the Euler?Euler model and the Euler?Lagrange model. Mathematical formulation of each of the model mentioned above and their merits and demerits are discussed. Detail reviews of different model used by different researchers with major results obtained by them are presented while the special focus is given on Euler?Euler and Euler?Lagrange CFD models.
The techno-economic performance analysis of biofuel production and electric power generation from biomass fast pyrolysis and bio-oil hydroprocessing is explored through process simulation. In this work, a process model of 72 MT/day pine wood fast pyrolysis and bio-oil hydroprocessing plant was developed with rate based chemical reactions using Aspen Plus® process simulator. It was observed from simulation results that 1 kg s?1 pine wooddb generate 0.64 kg s?1 bio-oil, 0.22 kg s?1 gas and 0.14 kg s?1 char. Simulation results also show that the energy required for drying and fast pyrolysis operations can be provided from the combustion of pyrolysis by-products, mainly, char and non-condensable gas with sufficient residual energy for miniature electric power generation. The intermediate bio-oil product from the fast pyrolysis process is upgraded into gasoline and diesel via a two-stage hydrotreating process, which was implemented by a pseudo-first order reaction of lumped bio-oil species followed by the hydrocracking process in this work. Simulation results indicate that about 0.24 kg s?1 of gasoline and diesel range products and 96 W of electric power can be produced from 1 kg s?1 pine wooddb. The effect of initial biomass moisture content on the amount of electric power generated and the effect of biomass feed composition on product yields were also reported in this study. Aspen Process Economic Analyser® was used for equipment sizing and cost estimation for an nth plant and the product value was estimated from discounted cash flow analysis assuming the plant operates for 20 years at a 10% annual discount rate. Economic analysis indicates that the plant will require £16.6 million of capital investment and product value is estimated at £6.25/GGE. Furthermore, the effect of key process and economic parameters on product value and the impact of electric power generation equipment on capital cost and energy efficiency were also discussed in this study.
In this paper a numerical study comparing the impingement behaviour of a hollow droplet and an analogous continuous droplet onto a substrate is presented. In the impingement model the transient flow dynamics during impact, spreading and solidification of the droplet are considered. The results of droplet spreading and solidification indicate that the impact process of the hollow droplet on the substrate is distinctly different from an analogous continuous droplet. The hollow droplet results in counter liquid jetting during the impact process, larger solidification time for the splat, smaller and thicker splat as compared to the analogous continuous droplet.
Papadikis K, Gu S, Bridgwater AV (2009) CFD modelling of the fast pyrolysis of biomass in fluidised bed reactors: Modelling the impact of biomass shrinkage, Chemical Engineering Journal 149 (1-3, 1 July 2009) pp. 417-427 Elsevier B.V.
The fluid?particle interaction and the impact of shrinkage on pyrolysis of biomass inside a 150 g/h fluidised bed reactor is modelled. Two 500 View the MathML sourcem in diameter biomass particles are injected into the fluidised bed with different shrinkage conditions. The two different conditions consist of (1) shrinkage equal to the volume left by the solid devolatilization, and (2) shrinkage parameters equal to approximately half of particle volume. The effect of shrinkage is analysed in terms of heat and momentum transfer as well as product yields, pyrolysis time and particle size considering spherical geometries. The Eulerian approach is used to model the bubbling behaviour of the sand, which is treated as a continuum. Heat transfer from the bubbling bed to the discrete biomass particle, as well as biomass reaction kinetics are modelled according to the literature. The particle motion inside the reactor is computed using drag laws, dependent on the local volume fraction of each phase. FLUENT 6.2 has been used as the modelling framework of the simulations with the whole pyrolysis model incorporated in the form of user defined function (UDF).
Bruchmüller J, van Wachem BGM, Gu S, Luo KH (2011) Modelling discrete fragmentation of brittle particles, Powder Technology 208 (3, 10 April 2011) pp. 731-739 Elsevier B.V.
A novel discrete fragmentation method (DFM) for spherical brittle particles using the discrete element method (DEM) has been developed, implemented and validated. Trajectories of individual fragments can be studied from the moment of breakage where the progeny might originate from incremental, simultaneous and/or repetitive fragmentation events. A particle breaks depending on the applied dynamic impact forces from collisions, the damage history, the particle size and material properties. This 3D model requires setting parameters solely dependent on the particle material and is consequently independent of any empirical value. Mass, momentum and energy is conserved during breakage. A theoretically consistent description from the onset of fragmentation to the cloud formation after breakage is provided and model outcomes have been compared to experimental results and other model predictions where very little deviation has been encountered. All material parameters have been varied independently to study the sensitivity of the model under dynamic fragmentation of numerous particles in a semi-autogenous mill.
Ranganathan P, Gu S (2016) Computational fluid dynamics modelling of biomass fast pyrolysis in fluidised bed reactors, focusing different kinetic schemes, BIORESOURCE TECHNOLOGY 213 pp. 333-341 ELSEVIER SCI LTD
Shen D, Xiao R, Gu S, Luo KH (2011) The pyrolytic behavior of cellulose in lignocellulosic biomass: a review, RSC Advances 1 (2011) pp. 1641-1660 Royal Society of Chemistry
Pyrolysis is estimated to be one of the most promising methods to convert biomass to diverse products (such as syn-gas, liquid fuel and charcoal), while its application has the potential for alleviating the fossil fuel crisis and environmental deterioration. Cellulose, a linear homopolymer of glucopyranose residues linked by ²-1, 4-glycosidic bonds, is the most principal component in biomass (accounting for more than 50% by weight). The research on the pyrolytic behavior of cellulose is particularly beneficial for achieving a better understanding of the pyrolytic behavior of biomass, also promoting its direct applications in terms of fuels, chemicals and bio-materials. The studies on pyrolysis of cellulose are extensively reported in the categories of the following four issues: (1) the physico-chemical properties of cellulose in lignocellulosic biomass; (2) the on-line pyrolysis study of cellulose; (3) the off-line pyrolysis study of cellulose; (4) the interactions with other chemical components under pyrolytic conditions. The information on pyrolysis of cellulose concerning the configuration of cellulose in biomass, the mass loss along with the evolution of volatiles against temperature, the yield of products, the proposed chemical pathways for cellulose decomposition and secondary cracking of the fragments would be vigorously discussed as well as the way-forward in this field, with thanks to the valuable contributions from the leading global researchers and their groups.
Papadikis K, Gu S, Bridgwater AV (2010) Geometrical Optimization of a Fast Pyrolysis Bubbling Fluidized Bed Reactor Using Comutational Fluid Dynamics, Energy & Fuels 24 (10 (2010)) pp. 5634-5651 ACS Publications
This paper analyzes the physical phenomena that take place inside an 1 kg/h bubbling fluidized bed reactor located at Aston University and presents a geometrically modified version of it, in order to improve certain hydrodynamic and gas flow characteristics. The bed uses, in its current operation, 40 L/min of N2 at 520 °C fed through a distributor plate and 15 L/min purge gas stream, i.e., N2 at 20 °C, via the feeding tube. The Eulerian model of FLUENT 6.3 is used for the simulation of the bed hydrodynamics, while the k ? õ model accounts for the effect of the turbulence field of one phase on the other. The three-dimensional simulation of the current operation of the reactor showed that a stationary bubble was formed next to the feeding tube. The size of the permanent bubble reaches up to the splash zone of the reactor, without any fluidizaton taking place underneath the feeder. The gas flow dynamics in the freeboard of the reactor is also analyzed. A modified version of the reactor is presented, simulated, and analyzed, together with a discussion on the impact of the flow dynamics on the fast pyrolysis of biomass.
Kumar A, Gu S (2012) Modelling impingement of hollow metal droplets onto a flat surface, International Journal of Heat and Fluid Flow 37 (October 2012) pp. 189-195 Elsevier B.V.
Despite many theoretical and experimental works dealing with the impact of dense melt droplets on the substrate during the process of thermal spray coating, the dynamics of the impingement of hollow melt droplet and the subsequent splat formation are not well addressed. In this paper a model study for the dynamic impingement of hollow droplet is presented. The hollow droplet is modelled such that it consists of a liquid shell enclosing a gas cavity. The impingement model considers the transient flow dynamics during impact, spreading and solidification of the droplet using the volume of fluid surface tracking method (VOF) coupled with a solidification model within a one-domain continuum formulation. The results for spreading, solidification and formation of splats clearly show that the impingement process of hollow droplet is distinctly different from the dense droplet. Study with different droplet void fractions and void distribution indicates that void fraction and void distribution have a significant influence on the flow dynamics during impact and on the final splat shape. The results are likely to provide insights for the less-explored behaviour of hollow melt droplets in thermal spray coating processes.
Sandwich panels with two-dimensional metal cores can be used to carry structural load as well as dissipate heat through solid conduction and forced convection. This work attempts to uncover the nature of heat transfer in these lightweight systems, with emphasis on the effects of varying cell morphologies and cell arrangements. The types of cell shape and cell arrangement considered include regular hexagon, square with connectivity 4 or 3, and triangle with connectivity 6 or 4. Two analytical models are developed: corrugated wall and effective medium. The former models the cellular structure in detail whilst, the latter models the fluid saturated porous structure using volume averaging techniques. The overall heat transfer coefficient and pressure drop are obtained as functions of relative density, cell shape, cell arrangement, fluid properties, and overall dimensions of the heat sink. A two-stage optimization is subsequently carried out to identify cell morphologies that optimize the structural and heat transfer performance at specified pumping power and at lowest weight. In the first stage, the overall heat transfer performance is optimized against relative density. Regular hexagonal cells are found to provide the highest levels of heat dissipation. In the second stage, a constraint on stiffness is added. It is then found that, for panels with thin cores, triangular cells constitute the most compact and yet stiff heat sink design; however, for high heat flux scenarios, hexagonal cells outperform triangular and square cells.
The pyrolytic behavior of wood is investigated under inert and oxidative conditions. The TGA experiment is given a temperature variation from 323 to 1173 K by setting the heating rate between 5 and 40 K/min. The results of DTG curves show that the hemicellulose shoulder peak for birch is more visible under inert atmosphere due to the higher content of reactive xylan-based hemicellulose (mannan-based for pine). When oxygen presents, thermal reactivity of biomass (especially the cellulose) is greatly enhanced due to the acceleration of mass loss in the first stage, and complex reactions occur simultaneously in the second stage when char and lignin oxidize. A new kinetic model is employed for biomass pyrolysis, namely the distributed activation energy model (DAEM). Under inert atmosphere, the distributed activation energy for the two species is found to be increased from 180 to 220 kJ/mol at the solid conversion of 10?85% with the high correlation coefficient. Under oxidative atmosphere, the distributed activation energy is about 175?235 kJ/mol at the solid conversion of 10?65% and 300?770 kJ/mol at the solid conversion of 70?95% with the low correlation coefficient (below 0.90). Comparatively, the activation energy obtained from established global kinetic model is correspondingly lower than that from DAEM under both inert and oxidative environments, giving relatively higher correlation coefficient (more than 0.96). The results imply that the DAEM is not suitable for oxidative pyrolysis of biomass (especially for the second mass loss stage in air), but it could represent the intrinsic mechanism of thermal decomposition of wood under nitrogen better than global kinetic model when it is applicable.
Mahrukh M, Kumar A, Gu S, Kamnis S, Gozali E (2016) Modeling the Effects of Concentration of Solid Nanoparticles in Liquid Feedstock Injection on High-Velocity Suspension Flame Spray Process, Industrial and Engineering Chemistry Research 55 (9) pp. 2556-2573
This paper presents the effects of the concentration of solid nanoparticles in the liquid feedstock injection on the high-velocity suspension flame spray (HVSFS) process. Four different concentrations of solid nanoparticles in suspension droplets with various droplet diameters are used to study gas dynamics, vaporization rate, and secondary breakup. Two types of injections, viz. surface and group, are used. The group-type injection increases the efficiency of droplet disintegration and the evaporation process and reduces the gas cooling. The initiation of the fragmentation process is difficult for small droplets carrying a high concentration of nanoparticles. Also, smaller droplets undergo rapid vaporization, leaving clogs of nanoparticles in the middle of the barrel. For larger droplets, severe fragmentation occurs inside the combustion chamber. For a higher concentration of nanoparticles, droplets exit the gun without complete evaporation. The results suggest that, in coating applications involving a higher concentration of nanoparticles, smaller droplet sizes are preferred.
Armstrong LM, Gu S, Luo KH (2010) The influence of multiple tubes on the tube-to-bed heat transfer in a fluidised bed, International Journal of Multiphase Flow 36 (11-12, November?December 2010) pp. 916-929 ScienceDirect
There have been few studies modelling both flow and heat transfer in fluidised beds. The kinetic theory of granular flow (KTGF) has been used for flow prediction in the past without heat transfer modelling. In the present study, a two-fluid Eulerian?Eulerian formulation incorporating the KTGF was applied first to a tube-to-bed reactor with one immersed tube and compared with the results in the literature. The bed was then modified to introduce two and three heated tubes. The effects on the flow and temperature distribution, local heat transfer coefficients and averaged heat transfer coefficients over a 3.0 s time period were carried out. Results showed that increasing the number of tubes promotes heat transfer from tubes to the particles and flow. The heat transfer coefficients extracted from the single-tube to three-tube cases were analysed in detail, confirming the importance of linking flow/particle and heat transfer calculations.
Power particles are mainly in solid state prior to impact on substrates from high velocity oxy-fuel (HVOF) thermal spraying. The bonding between particles and substrates is critical to ensure the quality of coating. Finite element analysis (FEA) models are developed to simulate the impingement process of solid particle impact on substrates. This numerical study examines the bonding mechanism between particles and substrates and establishes the critical particle impact parameters for bonding. Considering the morphology of particles, the shear-instability?based method is applied to all the particles, and the energy-based method is employed only for spherical particles. The particles are given the properties of widely used WC-Co powder for HVOF thermally sprayed coatings. The numerical results confirm that in the HVOF process, the kinetic energy of the particle prior to impact plays the most dominant role in particle stress localization and melting of the interfacial contact region. The critical impact parameters, such as particle velocity and temperature, are shown to be affected by the shape of particles, while higher impact velocity is required for highly nonspherical powder.
Duku MH, Gu S, Hagan EB (2011) Biochar production potential in Ghana-A review, Renewable & Sustainable Energy Reviews 15 (8, October 2011) pp. 3539-3551 Elsevier B.V.
Biochar is being promoted for its potential to improve soil properties, crop productivity and carbon sequestration in soil. Obstacles that may hinder rapid adoption of biochar production systems include technology and production costs, and feedstock availability. In this paper, a review of biochar production potential in Ghana is given. The availability of potential feedstock for biochar production such as agricultural residues, forestry residues, wood processing waste, the organic portion of municipal solid waste and livestock manure, together with a brief description of biomass conversion routes for biochar production is also given. Furthermore, potential agronomic and environmental benefits that can be derived from the application of biochar in soils are discussed. It is concluded that the large availability of biomass resources in Ghana gives a great potential for biochar production in the country.
Armstrong LM, Gu S, Luo KH (2010) Study of wall-to-bed heat transfer in a bubbling fluidised bed using the kinetic theory of granular flow, International Journal of Heat and Mass Transfer 53 (21-22, October 2010) pp. 4949-4959 Elsevier B.V.
Research into heat transfer modelling in fluidised beds is very limited due to its complexity. The kinetic theory of granular flow (KTGF) has been applied successfully to hydrodynamic modelling in the past but its application in heat transfer modelling has not been tested extensively. A two-fluid Eulerian?Eulerian model has been carried out applying the KTGF to a wall-to-bed reactor. The local heat transfer coefficients are compared against experimental data for two drag models, namely the Gidaspow and the Syamlal?O?Brien drag models. Furthermore, a parametric study is carried out for a variety of coefficients of restitution, particle diameter sizes and inlet velocities. Near wall analysis is carried out in both dense and dilute regions. Both drag models detect the passage of the bubble reasonably well but they predict the complete transition of the bubble past the sensors occurs at slightly different times. The heat transfer coefficients obtained with the Syamlal?O?Brien model showed more local fluctuations than the Gidaspow model because the Syamlal?O?Brien models was developed based on the particle terminal velocities which would indicate a slight sensitivity to a microscopic scale. Extension of the simulation for a longer period makes it possible to reveal that a periodic distribution occurred after 1.5 s and the local heat transfer coefficients gradually reduced to agree better with the experimental results which were previously over estimated. The study shows that a regular dynamic pattern is established in the bubbling fluidised bed only after 1.5?2 s.
Zeoli N, Gu S (2007) Computational validation of an isentropic plug nozzle design for gas atomisation, Computational Materials Science 42 (2, April 2008) pp. 245-258 ScienceDirect
During high pressure gas atomisation (HPGA), the molten metal stream is disintegrated to produce spherical powders when energy is transferred from the gas to the melt. Conventional annular-slit nozzle (ASN) in close-coupled atomisation generates an under-expanded gas jet with characteristic shock waves which consume a great deal of energy through expansion. An isentropic plug nozzle (IPN) is developed in this paper to reduce the shocks and maximize kinetic energy being transferred from the gas to instablize the melt stream. The performance of the IPN is examined using a numerical model which includes gas flow dynamics, droplet break-up mechanism and particle tracking. The numerical results demonstrate a good improvement of gas dynamics and powder yield from the IPN design in comparison with the ASN, in particular when hot gas is employed.
Shen DK, Gu S, Luo KH, Bridgwater AV (2009) Analysis of wood structural changes under thermal radiation, Energy & Fuels 23 (2 (2009)) pp. 1081-1088 ACS Publications
Experiment is carried out to observe the structural changes of cellulosic materials exposed to thermal radiation. To quantitatively analyze the results of pyrolyzed wood samples, simple geometric models are proposed to include both shrinkage and cracking. The shrinkage factors consider each direction of three-dimensional geometry, as well as the overall volume. The cracking coefficients include the depth and volume of cracks. The structural changes of the solid are characterized during the pyrolysis by varying the external heat flux and the species of wood. Formulas for calculation of crack depths are derived based on the experimental results for softwood and hardwood. The expressions of cracking can be incorporated into pyrolysis models to include the effects of cracks on heat and mass transfer during wood pyrolysis.
Bruchmüller J, Gu S, Luo KH, van Wachem BGM (2010) Discrete Element Method for Multiscale Modelling, Journal of Multiscale Modelling 02 (01n02, March & June 2010) World Scientific
A discrete element method (DEM) has been developed to provide highly accurate and detailed predictions of the Lagrangian particle phase. Especially in this study, DEM has been used together with an Eulerian approach for the fluid phase to look at interphase exchange phenomena in a multiphase-multiscale modeling approach. The drying process inside a fluidized bed coffee bean roaster has been chosen. Herein, heat, mass, and momentum transport are solved on a fluid cell level; heat, mass, and momentum transfer coefficients are solved at a particle scale level; and 1D temperature and moisture content profiles are solved inside each coffee bean on a sub-particle scale level. Therefore, this multiscale approach provides much more information compared to existing coffee bean roaster models. In this work, a detailed description of this method is provided and results on different scale levels have been discussed. Modeling data and experimental results are compared and found to be in good agreement.
Singh J, Gu S (2010) Commercialization potential of microalgae for bio fuels production, Renewable and Sustainable Energy Reviews 14 (9, December 2010) pp. 2596-2610 ScienceDirect
Microalgae feedstocks are gaining interest in the present day energy scenario due to their fast growth potential coupled with relatively high lipid, carbohydrate and nutrients contents. All of these properties render them an excellent source for biofuels such as biodiesel, bioethanol and biomethane; as well as a number of other valuable pharmaceutical and nutraceutical products. The present review is a critical appraisal of the commercialization potential of microalgae biofuels. The available literature on various aspects of microalgae, e.g. its cultivation, life cycle assessment, and conceptualization of an algal biorefinery, has been scanned and a critical analysis has been presented. A critical evaluation of the available information suggests that the economic viability of the process in terms of minimizing the operational and maintenance cost along with maximization of oil-rich microalgae production is the key factor, for successful commercialization of microalgae-based fuels.
Kishore N, Gu S (2011) Momentum and heat transfer phenomena of spheroid particles at moderate Reynolds and Prandtl numbers, International Journal of Heat and Mass Transfer 54 (11-12, May 2011) pp. 2595-2601 Elsevier B.V.
The momentum and heat transfer phenomena of spheroid particles in an unbounded Newtonian fluid have been numerically investigated by solving governing conservation equations of the mass, the momentum and the energy. The numerical solution methodology has been benchmarked by performing comparisons between present results with those reported in the literature. Further, extensive new results have been obtained to elucidate effects of pertinent dimensionless parameters such as the Reynolds number (Re), the Prandtl number (Pr) and the aspect ratio (e) on the flow and heat transfer behaviour of spheroid particles in the range of parameters: 1 } Re } 200; 1 } Pr } 1000 and 0.25 } e } 2.5. Regardless of the value of the Reynolds number, the total and individual drag coefficients of oblate spheroids (e 1). Irrespective of values of Reynolds and Peclet numbers, the average Nusselt number is large for prolate particles as compared to spheres and opposite trend has been observed for the case of oblate particles. Major contribution of this work is the development of simple correlations for the total drag coefficient and the average Nusselt number of unconfined isolated spheroid particles based on present numerical results which can be used in new applications.
Fischer?Tropsch synthesis (FTS) is a process which converts syn-gas (H2 and CO) to synthetic liquid fuels and valuable chemicals. Thermal gasification of biomass represents a convenient route to produce syn-gas from intractable materials particularly those derived from waste that are not cost effective to process for use in biocatalytic or other milder catalytic processes. The development of novel catalysts with high activity and selectivity is desirable as it leads to improved quality and value of FTS products. This review paper summarises recent developments in FT-catalyst design with regards to optimising catalyst activity and selectivity towards synthetic fuels.
Kamnis S, Gu S, Lu TJ, Chen C (2009) Numerical Modelling the Bonding Mechanism of HVOF Sprayed Particles, Computational Materials Science 46 (4, October 2009) pp. 1038-1043 Elsevier B.V.
During high velocity oxy-fuel (HVOF) thermal spraying, most powder particles remain in solid state prior to the formation of coating. A finite element (FE) model is developed to study the impact of thermally sprayed solid particles on substrates and to establish the critical particle impact parameters needed for adequate bonding. The particles are given the properties of widely used WC-Co powder for HVOF thermally sprayed coatings. The numerical results indicate that in HVOF process the kinetic energy of the particle prior to impact plays the most dominant role on particle stress localization and melting of the particle/substrate interfacial region. Both the shear-instability theory and an energy-based method are used to establish the critical impact parameters for HVOF sprayed particles, and it is found that only WC-Co particles smaller than 40 ¼m have sufficient kinetic and thermal energy for successful bonding.
Nabavi SA, Vladisavljevi? GT, Gu S, Ekanem EE (2015) Double emulsion production in glass capillary microfluidic device: Parametric investigation of droplet generation behaviour, Chemical Engineering Science 130 (7 July 2015) pp. 183-196 Elsevier B.V.
A three-phase axisymmetric numerical model based on Volume of Fluid?Continuum Surface Force (VOF?CSF) model was developed to perform parametric analysis of compound droplet production in three-phase glass capillary devices that combine co-flow and countercurrent flow focusing. The model predicted successfully generation of core?shell and multi-cored double emulsion droplets in dripping and jetting (narrowing and widening) regime and was used to investigate the effects of phase flow rates, fluid properties, and geometry on the size, morphology, and production rate of droplets. As the outer fluid flow rate increased, the size of compound droplets was reduced until a dripping-to-jetting transition occurred. By increasing the middle fluid flow rate, the size of compound droplets increased, which led to a widening jetting regime. The jetting was supressed by increasing the orifice size in the collection capillary or increasing the interfacial tension at the outer interface up to 0.06 N/m. The experimental and simulation results can be used to encapsulate CO2 solvents within gas-permeable microcapsules.
Sebastia-Saez D, Gu S, Ranganathan P, Papadikis K (2015) Meso-scale CFD study of the dry pressure drop, liquid hold-up, interfacial area and mass transfer of structured packing materials, International Journal of Greenhouse Gas Control 42 (November 2015) pp. 388-399 Elsevier B.V.
This work presents a meso-scale CFD methodology to describe the multiphase flow inside commercial structured packings for post-combustion CO2 capture.
Meso-scale simulations of structured packings are often limited in the literature to dry pressure drop analyses whereas mass transfer characteristics and gas?liquid interface tracking are usually investigated at micro-scale. This work aims at testing further capabilities of meso-scale modeling by implementing the interface tracking instead of analyzing only the dry pressure drop performance with single-phase simulations.
By doing so, it is possible to present also the hydrodynamics (i.e. liquid hold-up and interfacial area) for a small set of representative elementary units (REUs). The interest in interface tracking using commercial geometries lies on the fact that liquid hold-up and interfacial area have implications of capital importance on the overall performance of the absorber, hence the importance of developing a model to predict them accurately.
The results show how the relationship, reported in the literature, between the liquid load and both the liquid hold-up and the interfacial area is reproduced by the present CFD methodology. Also, a more realistic visualization is accomplished with images of the inner irregularities of the flow (i.e. liquid maldistribution, formation of droplets and rivulets, etc.), which lie far from the prevailing assumption of the formation of a perfectly developed liquid film over the packing.
Moreover, the effect of operating parameters such as the liquid load, liquid viscosity and liquid?solid contact angle on the amount of interfacial area available for mass transfer is also discussed.
Finally, mass source terms are also included to describe the gas absorption into the liquid phase hence testing all the capabilities of micro-scale modeling at meso-scale. The present model could be further used for the analysis and optimization of other structured packing geometries.
In the present work, the multiphase flow dynamics in fluidized beds is modelled using the Two-Fluid Model (TFM) where the characteristics of a granular solid phase are described by the Kinetic Theory of Granular Flow (KTGF). A drag function and heat transfer coefficients are used to describe the interaction and heat exchange between different phases, respectively. The effective thermal conductivity is defined as a function of phase volume fraction and thermal properties and is used to calculate the heat transfer coefficient from immersed tube to fluidized beds. The effects of different tube shapes on the flow characteristics and local heat transfer coefficients are investigated and the time-averaged heat-transfer coefficient is compared with the experimental data in the literature. The simulated results show that the heat transfer processes are significantly influenced by the reintroduction of solid particles around the immersed surfaces and the heat transfer coefficients vary sensitively with the distribution of the solid phase. The simulated heat transfer coefficients are in the same order as the experimental data which indicates that it can be quantitatively employed to aid the configuration of heating tubes during industrial design of the fluidized bed reactors.
Gu S, McCartney DG, Eastwick CN, Simmons KA (2003) Numerical Modelling of In-Flight Characteristics of Inconel 625 Particles during High Velocity Oxy-Fuel Thermal Spraying, Journal of Thermal Spray Technology 13 (2) pp. 200-213 Springer-Verlag
A computational fluid dynamics (CFD) model is developed to predict particle dynamic behavior in a high-velocity oxyfuel (HVOF) thermal spray gun in which premixed oxygen and propylene are burnt in a combustion chamber linked to a long, parallel-sided nozzle. The particle transport equations are solved in a Lagrangian manner and coupled with the two-dimensional, axisymmetric, steady state, chemically reacting, turbulent gas flow. Within the particle transport model, the total flow of the particle phase is modeled by tracking a small number of particles through the continuum gas flow, and each of these individual particles is tracked independently through the continuous phase. Three different combustion chamber designs were modeled, and the in-flight particle characteristics of Inconel were 625 studied. Results are presented to show the effect of process parameters, such as particle injection speed and location, total gas flow rate, fuel-to-oxygen gas ratio, and particle size on the particle dynamic behavior for a parallel-sided, 12 mm long combustion chamber. The results indicate that the momentum and heat transfer to particles are primarily influenced by total gas flow. The 12 mm long chamber can achieve an optimum performance for Inconel 625 powder particles ranging in diameter from 20 to 40 µm. At a particular spraying distance, an optimal size of particles is observed with respect to particle temperature. The effect of different combustion chamber dimensions on particle dynamics was also investigated. The results obtained for both a 22 mm long chamber and also one with a conical, converging design are compared with the baseline data for the 12 mm chamber.
Shen DK, Gu S, Bridgwater AV (2010) Study on the pyrolytic behaviour of xylan-based hemicellulose using TG-FTIR and Py-GC-FTIR, Journal of Analytical and Applied Pyrolysis 87 (2, March 2010) pp. 199-206 Copyright © 2016 Elsevier B.V. or its licensors or contributors.
Two sets of experiments, categorized as TG?FTIR and Py?GC?FTIR, are employed to investigate the mechanism of the hemicellulose pyrolysis and the formation of main gaseous and bio-oil products. The ?sharp mass loss stage? and the corresponding evolution of the volatile products are examined by the TG?FTIR graphs at the heating rate of 3?80 K/min. A pyrolysis unit, composed of fluidized bed reactor, carbon filter, vapour condensing system and gas storage, is employed to investigate the products of the hemicellulose pyrolysis under different temperatures (400?690 °C) at the feeding flow rate of 600 l/h. The effects of temperature on the condensable products are examined thoroughly. The possible routes for the formation of the products are systematically proposed from the primary decomposition of the three types of unit (xylan, O-acetylxylan and 4-O-methylglucuronic acid) and the secondary reactions of the fragments. It is found that the formation of CO is enhanced with elevated temperature, while slight change is observed for the yield of CO2 which is the predominant products in the gaseous mixture.
Sebastia-Saez D, Gu S, Ranganathan P, Papadikis K (2013) 3D modeling of hydrodynamics and physical mass transfer characteristics of liquid film flows in structured packing elements, International Journal of Greenhouse Gas Control 19 (November 2013) pp. 492-502 Elsevier B.V.
Post-combustion CO2 capture by chemical absorption in structured packed columns has been technically and commercially proven as a viable option to be deployed for carbon emissions mitigation. In this work, a three dimensional CFD model at small scale for hydrodynamics and physical mass transfer in structured packing elements is developed. The results from the present model are validated with theory and reported experimental data. For hydrodynamics, the liquid film thickness and wetted area are calculated whereas for mass transfer, the Sherwood number and concentrations of dissolved species are predicted. The CFD results match reasonably with experimental and theoretical data. Furthermore, the influence of texture patterns and the liquid phase viscosity on the wetted area is studied. It is found that both parameters have a strong influence on the results. For physical mass transfer, the study of the transient behavior and the impact of the liquid load on the absorption rate is assessed. It is observed that lower liquid loads maximize mass transfer coefficients but also enhance liquid misdistribution (i.e. with the possibility of hindering mass transfer). An optimum liquid load is found where the effect of liquid misdistribution can be avoided, maximizing gas absorption.
Duku MH, Gu S, Hagan EB (2010) A comprehensive review of biomass resources and biofuels potential in Ghana, Renewable and Sustainable Energy Reviews 15 (1, January 2011) pp. 404-415 ScienceDirect
Biomass is the major energy source in Ghana contributing about 64% of Ghana's primary energy supply. In this paper, an assessment of biomass resources and biofuels production potential in Ghana is given. The broad areas of energy crops, agricultural crop residues, forest products residues, urban wastes and animal wastes are included. Animal wastes are limited to those produced by domesticated livestock. Agricultural residues included those generated from sugarcane, maize, rice, cocoa, oil palm, coconut, sorghum and millet processing. The urban category is subdivided into municipal solid waste, food waste, sewage sludge or bio-solids and waste grease. The availability of these types of biomass, together with a brief description of possible biomass conversion routes, sustainability measures, and current research and development activities in Ghana is given. It is concluded that a large availability of biomass in Ghana gives a great potential for biofuels production from these biomass resources.
The rapid depletion of conventional fossil fuels and day-by-day growth of environmental pollution due to use of extensive use of fossil fuels have raised concerns over the use of the fossil fuels; and thus search for alternate renewable and sustainable sources for fuels has started in the last few decades. In this context biomass derived fuels seems to be the promising path; and various routes are available for the biomass processing such as pyrolysis, transesterification, hydrothermal liquefaction, steam reforming, etc.; and the hydrothermal liquefaction (HTL) of wet biomass seems to be the promising route. Therefore, this article briefly enlightened a few concepts of HTL such as the elemental composition of bio-crude obtained by HTL, different types of feedstock adopted for HTL, mechanism of HTL processes, possible process flow diagrams for HTL of both wet and dry biomass and energy efficiency of the process. In addition, this article also enlisted possible future research scope for concerned researchers and a few of them are setting up HTL plant suitable for both wet and dry biomass feedstock; analysing influence of parameters such as temperature, pressure, residence time, catalytic effects, etc.; deriving optimized pathways for better conversion; and development of theoretical models representing the process to the best possible accuracy depending on nature of feedstock.
Papadikis K, Gu S, Bridgwater AV (2009) Computational modelling of the impact of particle size to the heat transfer coefficient between biomass particles and a fluidised bed, Fuel Processing Technology 91 (1, January 2010) pp. 68-79 Elsevier B.V.
The fluid?particle interaction and the impact of different heat transfer conditions on pyrolysis of biomass inside a 150 g/h fluidised bed reactor are modelled. Two different size biomass particles (350 ¼m and 550 ¼m in diameter) are injected into the fluidised bed. The different biomass particle sizes result in different heat transfer conditions. This is due to the fact that the 350 ¼m diameter particle is smaller than the sand particles of the reactor (440 ¼m), while the 550 ¼m one is larger. The bed-to-particle heat transfer for both cases is calculated according to the literature. Conductive heat transfer is assumed for the larger biomass particle (550 ¼m) inside the bed, while biomass?sand contacts for the smaller biomass particle (350 ¼m) were considered unimportant. The Eulerian approach is used to model the bubbling behaviour of the sand, which is treated as a continuum. Biomass reaction kinetics is modelled according to the literature using a two-stage, semi-global model which takes into account secondary reactions. The particle motion inside the reactor is computed using drag laws, dependent on the local volume fraction of each phase. FLUENT 6.2 has been used as the modelling framework of the simulations with the whole pyrolysis model incorporated in the form of User Defined Function (UDF).
Depletion of oil resources and increase in energy demand have driven the researchers to seek ways to convert the waste products into high quality oils that could replace fossil fuels. Plastic waste is in abundance and can be converted into high quality oil through the pyrolysis process. In this study, pyrolysis oils were produced from polyethylene (LDPE700), the most common used plastic, and ethylene-vinyl acetate (EVA900) at pyrolysis temperatures of 700oC and 900oC respectively. The oils were then tested in a four cylinder diesel engine, and the performance, combustion and emission characteristics were analysed in comparison with mineral diesel. It was found that the engine could operate on both oils without the addition of diesel. LDPE700 exhibited almost identical combustion characteristics and brake thermal e ciency to that of diesel operation, with lower NOX, CO and CO2 emissions but higher unburned hydrocarbons (UHC). On the contrary, EVA900 presented longer ignition delay period, lower e ciency (1.5?2%), higher NOX and UHC emissions and lower CO and CO2 in comparison to diesel. The addition of diesel to the EVA900 did not significantly improve the overall engine performance.
Flameless combustion has been developed to reduce emissions whilst retaining thermal efficiencies in combustion systems. It is characterized with its distinguished features, such as suppressed pollutant emission, homogeneous temperature distribution, reduced noise and thermal stress for burners and less restriction on fuels (since no flame stability is required). Recent research has shown the potential of flameless combustion in the power generation industry such as gas turbines. In spite of its potential, this technology needs further research and development to improve its versatility in using liquid fuels as a source of energy. In this review, progress toward application of the flameless technique is presented with emphasis on gas turbines. A systematic analysis of the state-of-the-art and the major technical and physical challenges in operating gas turbines with liquid fuels in a flameless combustion mode is presented. Combustion characteristics of flameless combustion are explained along with a thorough review of modelling and simulation of the liquid fuel fed flameless combustion. A special focus is given to the relevant research on applications to the inner turbine burners. The paper is concluded by highlighting recent findings and pointing out several further research directions to improve the flameless combustion application in gas turbines, including in-depth flow and combustion mechanisms, advanced modelling, developed experimental technology and comprehensive design methods aiming at gas turbine flameless combustors.
In this study, the effect of potassium on the cellulose fast pyrolysis in fluidized bed reactor has been studied using Computational Fluid Dynamics (CFD). A multiphase pyrolysis model of cellulose has been implemented by integrating the hydrodynamics of the fluidized bed with an adjusted cellulose pyrolysis mechanism that accounts the effect of potassium. The model has been validated with the reported experimental data. The simulation results show that potassium concentration and reactor temperature have a significant effect on the yields and components of cellulose pyrolysis products. The product yields fluctuate is caused by the unstable flow in the fluidized bed. The result shows that the increased potassium concentration in the cellulose causes a significant increase of the gas and char yields and reduction in the bio-oil. Also, the dramatic composition variations in bio-oil and gas were observed due to the inhibition of fragmentation, and the depolymerization reaction of activated cellulose, and the catalysis of the depolymerization reaction of cellulose. It is also found that the increase in reactor temperature greatly enhances the endothermic pyrolysis reaction, which leads to the significant changes in the yield and composition of cellulose pyrolysis products.
Plastic waste is an ideal source of energy due to its high heating value and abundance. It can be converted into oil through the pyrolysis process and utilised in internal combustion engines to produce power and heat. In the present work, plastic pyrolysis oil is manufactured via a fast pyrolysis process using a feedstock consisting of different types of plastic. The oil was analysed and it was found that its properties are similar to diesel fuel. The plastic pyrolysis oil was tested on a four-cylinder direct injection diesel engine running at various blends of plastic pyrolysis oil and diesel fuel from 0% to 100% at different engine loads from 25% to 100%. The engine combustion characteristics, performance and exhaust emissions were analysed and compared with diesel fuel operation. The results showed that the engine is able to run on plastic pyrolysis oil at high loads presenting similar performance to diesel while at lower loads the longer ignition delay period causes stability issues. The brake thermal efficiency for plastic pyrolysis oil at full load was slightly lower than diesel, but NOX emissions were considerably higher. The results suggested that the plastic pyrolysis oil is a promising alternative fuel for certain engine application at certain operation conditions.
A comprehensive 3D coupled mathematical model is developed to study the microwave assisted thermocatalytic decomposition of methane with activated carbon as the catalyst. A simple reaction kinetic model for methane conversion (accounting for catalyst deactivation) is developed from previously published experimental data and coupled with the governing equations for the microwaves, heat transfer, mass transfer and fluid flow physics. Temperature distribution and concentration profiles of CH4 & H2 in the catalyst bed are presented. The temperature profiles at di erent input power values predict a non-uniform temperature distribution with hot-spots near the top and bottom of the catalyst. The concentration profiles predict a linear variation of CH4 and H2 concentration along the length of the reactor and show a good agreement with experimental conversion values. The influence of volumetric hourly space velocity on methane conversion is also investigated.
This paper presents the investigation of engine optimisation when plastic pyrolysis oil (PPO) is used as the primary fuel of a direct injection diesel engine. Our previous investigation revealed that PPO is a promising fuel however the results suggested that control parameters should be optimised in order to obtain a better engine performance. In the present work, the injection timing was advanced, and fuel additives were utilised to overcome the issues experienced in the previous work. In addition, spray characteristics of PPO were investigated in comparison with diesel to provide in-depth understanding of the engine behaviour. The experimental results on advanced injection timing (AIT) showed a reduced brake thermal efficiency and increased carbon monoxide, unburned hydrocarbons and nitrogen oxides emissions in comparison to standard injection timing. On the other hand, the addition of fuel additive resulted in a higher engine efficiency and lower exhaust emissions. Finally, the spray tests revealed that the spray tip penetration for PPO is faster than diesel. The results suggested that AIT is not a preferable option while fuel additive is a promising solution for long-term use of PPO in diesel engines.
Biofuels have been identified as a mid-term GHG emission abatement solution for decarbonising the transport sector. This study examines the techno-economic analysis of biofuel production via biomass fast pyrolysis and subsequent bio-oil upgrading via zeolite cracking. The aim of this study is to compare the techno-economic feasibility of two conceptual catalyst regeneration configurations for the zeolite cracking process: (i) a two-stage regenerator operating sequentially in partial and complete combustion modes (P-2RG) and (ii) a single stage regenerator operating in complete combustion mode coupled with a catalyst cooler (P-1RGC). The designs were implemented in Aspen Plus® based on a hypothetical 72 t/day pine wood fast pyrolysis and zeolite cracking plant and compared in terms of energy efficiency and profitability. The energy efficiencies of P-2RG and P-1RGC were estimated at 54% and 52%, respectively with corresponding minimum fuel selling prices (MFSPs) of £7.48/GGE and £7.20/GGE. Sensitivity analysis revealed that the MFSPs of both designs are mainly sensitive to variations in fuel yield, operating cost and income tax. Furthermore, uncertainty analysis indicated that the likely range of the MFSPs of P-1RGC (£5.81/GGE - £11.63/GGE) at 95% probability was more economically favourable compared with P-2RG, along with a penalty of 2% reduction in energy efficiency. The results provide evidence to support the economic viability of biofuel production via zeolite cracking of pyrolysis-derived bio-oil.
When a complex geometry is rotated in front of the thermal spray gun, the following kinematic parameters vary in a coupled fashion dictated by the geometry: Stand-off distance, spray angle and gun traverse speed. These fluctuations affect the conditions of particle impact with major implications on the coating?s properties. This work aims to probe into the interplay and isolated effect of these parameters on vital coating characteristics in applications requiring variable stand-off distance and spray angles. WC-17Co powders are sprayed via HVOF on steel substrates in a set of experiments that simulates the spray process of a non-circular cross section, while it allows for individual control of the kinematic parameters. Comprehensive investigation of their influence is made on deposition rate, residual stresses, porosity and microhardness of the final coating. It was determined that oblique spray angles and long stand-off distances compromise the coating properties but in some cases, the interplay of the kinematic parameters produced non-linear behaviours. Microhardness is related negatively with oblique spray angles at short distances while a positive correlation emerges as the stand-off distance is increased. Porosity and residual stresses are sensitive to the spray angle only in relatively short stand-off distances.
Chemical recycling is an attractive way to address the explosive growth of plastic waste and disposal problems. Pyrolysis is a chemical recycling process that can convert plastics into high quality oil, which can then be utilised in internal combustion engines for power and heat generation. The aim of the present work is to evaluate the potential of using oils that have been derived from the pyrolysis of plastics at di erent temperatures in diesel engines. The produced oils were analysed and found to have similar properties to diesel fuel. The plastic pyrolysis oils were then tested in a four-cylinder direct injection diesel engine, and their combustion, performance and emission characteristics analysed and compared to mineral diesel. The engine was found to perform better on the pyrolysis oils at higher loads. The pyrolysis temperature had a signi cant e ect, as the oil produced at a lower temperature presented higher brake thermal e ciency and shorter ignition delay period at all loads. This oil also produced lower NOX, UHC, CO and CO2 emissions than the oil produced at a higher temperature, although diesel emissions were lower.
This study examines the GHG emissions associated with producing bio-hydrocarbons via fast pyrolysis of Miscanthus. The feedstock is then upgraded to bio-oil products via hydroprocessing and zeolite cracking. Inventory data for this study were obtained from current commercial cultivation practices of Miscanthus in the UK and state-of-the-art process models developed in Aspen Plus®. The system boundary considered spans from the cultivation of Miscanthus to conversion of the pyrolysis-derived bio-oil into bio-hydrocarbons up to the refinery gate. The Miscanthus cultivation subsystem considers three scenarios for soil organic carbon (SOC) sequestration rates. These were assumed as follows: (i) excluding (SOC), (ii) low SOC and (iii) high (SOC) for best and worst cases. Overall, Miscanthus cultivation contributed moderate to negative values to GHG emissions, from analysis of excluding SOC to high SOC scenarios. Furthermore, the rate of SOC in the Miscanthus cultivation subsystem has significant effects on total GHG emissions. Where SOC is excluded, the fast pyrolysis subsystem shows the highest positive contribution to GHG emissions, while the credit for exported electricity was the main ?negative? GHG emission contributor for both upgrading pathways. Comparison between the bio-hydrocarbons produced from the two upgrading routes and fossil fuels indicates GHG emission savings between 68 and 87%. Sensitivity analysis reveals that bio-hydrocarbon yield and nitrogen gas feed to the fast pyrolysis reactor are the main parameters that influence the total GHG emissions for both pathways.
This paper evidences the viability of chemical recycling of CO2 via reverse water-gas shift reaction using advanced heterogeneous catalysts. In particular, we have developed a multicomponent Fe-Cu-Cs/Al2O3 catalyst able to reach high levels of CO2 conversions and complete selectivity to CO at various reaction conditions (temperature and space velocities). In addition, to the excellent activity, the novel-Cs doped catalyst is fairly stable for continuous operation which suggests its viability for deeper studies in the reverse water-gas shift reaction. The catalytic activity and selectivity of this new material have been carefully compared to that of Fe/Al2O3, Fe-Cu/Al2O3 and Fe-Cs/Al2O3 in order to understand each active component?s contribution to the catalyst?s performance. This comparison provides some clues to explain the superiority of the multicomponent Fe-Cu-Cs/Al2O3 catalyst
In this study, plasma-catalytic steam reforming of toluene as a biomass tar model compound was carried out in a coaxial dielectric barrier discharge (DBD) plasma reactor. The effect of Ni/Al2O3 catalysts with different nickel loadings (5?20 wt%) on the plasma-catalytic gas cleaning process was evaluated in terms of toluene conversion, gas yield, by-products formation and energy efficiency of the plasma-catalytic process. Compared to the plasma reaction without a catalyst, the combination of DBD with the Ni/Al2O3 catalysts significantly enhanced the toluene conversion, hydrogen yield and energy efficiency of the hybrid plasma process, while significantly reduced the production of organic by-products. Increasing Ni loading of the catalyst improved the performance of the plasma-catalytic processing of toluene, with the highest toluene conversion of 52% and energy efficiency of 2.6 g/kWh when placing the 20 wt% Ni/Al2O3 catalyst in the plasma. The possible reaction pathways in the hybrid plasma-catalytic process were proposed through the combined analysis of both gas and liquid products.
The aim of this study is to evaluate comprehensively the effect of spray angle, spray distance and gun traverse speed on the microstructure and phase composition of HVOF sprayed WC-17 coatings. An experimental setup that enables the isolation of each one of the kinematic parameters and the systemic study of their interplay is employed. A mechanism of particle partition and WC-cluster rebounding at short distances and oblique spray angles is proposed. It is revealed that small angle inclinations benefit notably the WC distribution in the coatings sprayed at long stand-off distances. Gun traverse speed, affects the oxygen content in the coating via cumulative superficial oxide scales formed on the as-sprayed coating surface during deposition. Metallic W continuous rims are seen to engulf small splats, suggesting crystallization that occurred in-flight.
An Eulerian-Eulerian multi-phase CFD model was set up to simulate a lab-scale fluidized bed reactor for the fast pyrolysis of biomass. Biomass particles and the bed material (sand) were considered to be particulate phases and modelled using the kinetic theory of granular flow. A global, multi-stage chemical kinetic mechanism was integrated into the main framework of the CFD model and employed to account for the process of biomass devolatilization. A 3-parameter shrinkage model was used to describe the variation in particle size due to biomass decomposition. This particle shrinkage model was then used in combination with a quadrature method of moment (QMOM) to solve the particle population balance equation (PBE). The evolution of biomass particle size in the fluidized bed was obtained for several different patterns of particle shrinkage, which were represented by different values of shrinkage factors. In addition, pore formation inside the biomass particle was simulated for these shrinkage patterns, and thus, the density variation of biomass particles is taken into account.
The solution precursor thermal spraying (SPTS) process is used to obtain nano-sized dense coating
layers. During the SPTS process, the in situ formation of nanoparticles is mainly dependent on
combustion gas-temperature, gas-pressure, gas-velocity, torch design, fuel type, and Oxygen-Fuel
(O/F) mixture ratios, precursor injection feeding ratio and flow rates, properties of fuel and
precursor and its concentration, and the precursor droplets fragmentation. The focus of the present
work is the numerical study of atomization of pure solvent droplets streams into fine droplets spray
using an effervescent twin-fluid atomizer. For better droplet disintegration appropriate atomization
techniques can be used for injecting the precursor in the CH-2000 high-velocity oxygen fuel
(HVOF) torch. The CFD computations of the SPTS process are essentially required because the
internal flow physics of HVOF process cannot be examined experimentally. In this research for the
first time, an effervescent twin-fluid injection nozzle is designed to inject the solution precursor into
the HVOF torch, and the effects on the HVOF flame dynamics are analyzed. The computational
fluid dynamics (CFD) modeling is performed using Linearized Instability Sheet Atomization
(LISA) model and validated by the measured values of droplets size distribution at varied Gas-to-
Liquid flow rate Ratios (GLR). Different nozzle diameters with varied injection parameters are
numerically tested, and results are compared to observe the effects on the droplet disintegration and
evaporation. It is concluded that the effervescent atomization nozzle used in the CH-2000 HVOF
torch can work efficiently even with bigger exit diameters and with higher values of viscosity and
surface-tension of the solution. It can generate smaller size precursor droplets (2 ¼m
could help in the formation of fine nanostructured coatings.
The aim of this study is to evaluate comprehensively the effect of spray angle, spray distance and gun traverse
speed on the microstructure and phase composition of HVOF sprayed WC-17 coatings. An experimental setup
that enables the isolation of each one of the kinematic parameters and the systemic study of their interplay is
employed. A mechanism of particle partition and WC-cluster rebounding at short distances and oblique spray
angles is proposed. It is revealed that small angle inclinations benefit notably the WC distribution in the coatings
sprayed at long stand-off distances. Gun traverse speed, affects the oxygen content in the coating via cumulative
superficial oxide scales formed on the as-sprayed coating surface during deposition. Metallic W continuous rims
are seen to engulf small splats, suggesting crystallization that occurred in-flight.
Droplets and rivulets over solid surfaces play an important role in a number of engineering applications. We use a Computational Fluid Dynamics model consisting in a smooth inclined plate to study the effect of the contact angle on the morphology, residence time and mass transfer into liquid rivulets. Measurements of the contact angle?using the sessile drop method?between aqueous monoethanolamine solutions and two commercial surfaces used for gas separation, are introduced as boundary condition. Reducing the contact angle from 60° to 20° flattens the rivulet, increasing the gas-liquid interface area by 85%. The cumulative residence time broadens, with an increase of 12% in Ä10, and of 37% in Ä90. There is consequently, a theoretical increase of 68% in the total mass transfer rate. A sensible design of the liquid-solid interaction is therefore crucial to good mass transfer performance.
Polypropylene is the most common type of plastic found in municipal solid waste. The production of polypropylene is expected
to increase due to the widespread utilization in daily life, resulting in even higher amounts of polypropylene waste. Sending this
plastic to landfill not only exacerbates environmental problems, but also results in energy loss due to the elevated energy content of
polypropylene. Pyrolysis is a process that can effectively convert polypropylene waste into fuel, which can then be used to generate
power and heat. In the present study, the ect of the pyrolysis temperature on the pyrolysis of polypropylene was investigated, and
the oils produced at 700oC (PP700) and 900oC (PP900) were used to fuel a four cylinder diesel engine. The engine's combustion,
performance and emission characteristics were analysed and compared to diesel operation. The results showed that both PP700
and PP900 enabled stable engine operation, with PP900 performing slightly better in terms of efficiency and emissions. However,
PP700 and PP900 were found to have longer ignition delay periods, longer combustion periods, lower brake thermal efficiencies,
higher NOX, UHC and CO emissions, and lower CO2 emissions in comparison to diesel operation. Nonetheless, the addition of a
small quantity of diesel improved the overall performance of the oil blends, resulting in comparable results to diesel in the case of
In this work, a two-dimensional numerical
fluid model is developed for a partially
packed dielectric barrier discharge (DBD) in pure helium. In
fluence of packing on
the discharge characteristics is studied by comparing the results of DBD with partial
packing with those obtained for DBD with no packing. In the axial partial packing
configuration studied in this work, the electric field strength was shown to be en
hanced at the top surface of the spherical packing material and at the contact points
between the packing and the dielectric layer. For each value of applied potential,
DBD with partial packing showed an increase in the number of pulses in the current
profile in the positive half cycle of the applied voltage, as compared to DBD with
no packing. Addition of partial packing to the plasma-alone DBD also led to an
increase in the electron and ion number densities at the moment of breakdown. The
time averaged electron energy profiles showed that a much higher range of electron
energy can be achieved with the use of partial packing as compared to no packing
in a DBD, at the same applied power. The spatially and time averaged values over
one voltage cycle also showed an increase in power density and electron energy on
inclusion of partial packing in the DBD. For the applied voltage parameters studied
in this work, the discharge was found to be consistently homogeneous and showed
the characteristics of atmospheric pressure glow discharge.
Catalytic upgrading of biomass pyrolysis vapours is a potential method for the production of hydrocarbon fuel intermediates. This work attempts to study the catalytic upgrading of pyrolysis vapours in a pilot scale FCC riser in terms of hydrodynamics, Residence Time Distribution (RTD) and chemical reactions by CFD simulation. NREL?s Davison Circulating Riser (DCR) reactor was used for this investigation. CFD simulation was performed using 2-D Eulerian?Eulerian method which is computationally less demanding than the alternative Euler-Lagrangian method. First, the hydrodynamic model of the riser reactor was validated with the experimental results. A single study of time-averaged solid volume fraction and pressure drop datas was used for the validation. The validated hydrodynamic model was extended to simulate hydrodynamic behaviors and catalyst RTD in the Davison Circulating Riser (DCR) reactor. Furthermore, the effects on catalyst RTD were investigated for optimising catalyst performance by varying gas and catalyst flow rates. Finally, the catalytic upgrading of pyrolysis vapours in the DCR riser was attempted for the first time by coupling CFD model with kinetics. A kinetic model for pyrolysis vapours upgrading using a lumping kinetic approach was implemented to quantify the yields of products. Five lumping components, including aromatic hydrocarbons, coke, non?condensable gas, aqueous fraction, and non?volatile heavy compounds (residue) were considered. It was found that the yield of lumping components obtained from the present kinetic model is very low. Thus, the further research needs to be carried out in the area of the kinetic model development to improve the yield prediction.
Herein, the production of synthetic natural gas is proposed as an effective route for CO2 conversion. Typical catalysts for this reaction are based on Ni. In this study, we demonstrated that the addition of promoters such as iron and cobalt can greatly benefit the activity of standard Ni methanation catalysts. In particular cobalt seems to be a very efficient promoter. Our Co doped material is an outstanding catalysts for the CO2 methanation leading to high levels of CO2 conversion with selectivities close to 100%. Additionally, this catalyst is able to preserve excellent performance at relatively high space velocity which allows flexibility in the reactor design making easier the development of compact CO2 utilisation units. As an additional advantage, the Co-promoted catalysts is exceptionally stable conserving high levels of CO2 conversion under continuous operations in long terms runs.
The morphology of gravity-driven rivulets affects the mass transfer performance
in gas separation processes, hence, the need for an improved knowledge on the
hydrodynamics of this
ow. It is well established that the interface area of
the rivulets is determined by the balance between inertia and surface tension,
i.e. the Weber number, which in light of the results presented here, are not
the only parameters involved, but also the inclination of the plate has an effect
on the balance of forces which determines the amount of gas-liquid interface
area. The analysis of the interface area in rivulet
ow demands, therefore, a
more complete physical explanation for packing design purposes. In this work,
we analyse the combined effect of both the inertia and the inclination of the
plate in the interface area of liquid rivulets using CFD and the Volume-of-Fluid
interface tracking method. As a result, we propose the use of the Froude number
to provide a more complete physical explanation on the interface area formation
of gravity-driven liquid rivulets.
An introduction and overview of the work is given in Chapter 1. In Chapter 2, a description of the equipment and the kinetics modelling used in this thesis is explained in detail. Chapter 3 includes an overview of traditional solvents and shows the kinetics and mass
transfer results of the absorption of CO2 in amine solvents. Chapter 4 starts with a literature review on organic solvents and hybrid solutions (organic-amine aqueous solutions) and includes the mass transfer and
kinetic results of the absorption of CO2 in selected hybrid solvents containing amines. Chapters 3 and 4 sum up the 11 solutions tested for the absorption of CO2
and include their physical characterization (density, viscosity and N2O solubility), at unloaded and loaded conditions and from 298 to 353K. Chapter 5 is focused on the thermodynamic modelling of new amine solvents in ASPEN PLUS and Chapter 6 includes the modelling at pilot plant scale of absorber and desorber. Every chapter includes conclusions and final remarks are given at the end of this thesis. Chapter 7 presents the conclusions of the whole thesis and recommendations for future work.
Polymer electrolyte membrane (PEM) fuel cells have higher efficiency and energy density and are capable of rapidly adjusting to power demands. Effective water management is one of the key issues for increasing the efficiency of PEMFC. In the current study, a three-dimensional (3D) lattice Boltzmann model is developed to simulate the water transport and oxygen diffusion in the gas diffusion layer (GDL) of PEM fuel cells with electrochemical reaction on the catalyst layer taken into account. In this paper, we demonstrate that this model is able to predict the liquid and gas flow fields within the 3D GDL structure and how they change with time. With the two-phase flow and electrochemical reaction coupled in the model, concentration of oxygen through the GDL and current density distribution can also be predicted. The model is then used to investigate the effect of microporous layer on the cell performance in 2D to reduce the computational cost. The results clearly show that the liquid water content can be reduced with the existence of microporous layer and thus the current density can be increased.
The chemical absorption process has been extensively studied as one of the main carbon capture and separation
technologies. This process comprises two stages: The absorption of CO2 into the solvent and the desorption, to
regenerate the solvent and produce the high concentrated CO2 gas.
Validated simulation models are essential for the scale-up of the chemical absorption process and they are
typically validated using only data from one pilot plant. In this work, a simulation model of the desorption
column built in ASPEN PLUS v8.6 was validated using four experimental pilot campaigns using 30 wt% MEA.
The desorbers in the different campaigns varied in the diameters, structured packing heights and packing types.
A good agreement is observed between experimental data and the simulation results of the chemical absorption
process presented here. The model shows an AARD (average absolute relative deviation) of 9.2% for the
CO2 stripped (kg/h) for the tested 78 experimental runs. The simulated temperatures of the liquid flux leaving
the reboiler show a deviation of 3.3% compared with the experimental data. The deviations on the estimation of
the CO2 stripped show some dependency on the CO2 loading in the rich amine flux entering the desorber.
However, the deviations are independent on the temperature of the rich amine
Polymer electrolyte membrane(PEM) fuel cells have higher efficiency and energy
density and are capable of rapidly adjusting to power demands. Effective water
management is one of the key issues for increasing the efficiency of PEMFC. In the
current study, a three-dimensional(3D) lattice Boltzmann model is developed to
simulate the water transport and oxygen diffusion in the gas diffusion layer(GDL)
of PEM fuel cells with electrochemical reaction on the catalyst layer taken into
account. In this paper, we demonstrate that this model is able to predict the
liquid and gas flow fields within the 3D GDL structure and how they change with
time. With the two-phase flow and electrochemical reaction coupled in the model,
concentration of oxygen through the GDL and current density distribution can also
be predicted. The model is then used to investigate the effect of microporous layer
on the cell performance in 2D to reduce the computational cost. The results clearly
show that the liquid water content can be reduced with the existence of microporous
layer and thus the current density can be increased.
This review presents the developments in the mathematical models for various
bioelectrochemical systems. A number of modeling approaches starting
with the simple description of biological and electrochemical processes in
terms of ordinary differential equations to very detailed 2D and 3D models
that study the spatial distribution of substrates and biomass, have been
developed to study BES performance. Additionally, mathematical models
focused on studying a particular process such as ion diffusion through membrane
and new modeling approaches such as artifcial intelligence methods,
cellular network models, etc., have also been described. While most mathematical
models are still focused on performance studies and optimization of
microbial fuel cells, new models to study other BESs such as microbial electrolysis
cell, microbial electrosynthesis and microbial desalination cell have
also been reported and discussed in this review.
A novel framework integrating dynamic simulation (DS), life cycle assessment (LCA) and techno-economic assessment (TEA) of bioelectrochemical system (BES) has been developed to study for the first time wastewater treatment by removal of chemical oxygen demand (COD) by oxidation in anode and thereby harvesting electron and proton for carbon dioxide reduction reaction or reuse to produce products in cathode. Increases in initial COD and applied potential increase COD removal and production (in this case formic acid) rates. DS correlations are used in LCA and TEA for holistic performance analyses. The cost of production of HCOOH is ¬0.015?0.005g?1 for its production rate of 0.094?0.26kgyr?1 and a COD removal rate of 0.038?0.106kgyr?1. The life cycle (LC) benefits by avoiding fossil-based formic acid production (93%) and electricity for wastewater treatment (12%) outweigh LC costs of operation and assemblage of BES (?5%), giving a net 61MJkg-1HCOOH saving.
In the context of Carbon Capture and Utilisation (CCU), the catalytic reduction of CO2 to CO via reverse water-gas shift (RWGS) reaction is a desirable route for CO2 valorisation. Herein, we have developed highly effective Ni-based catalysts for this reaction. Our study reveals that CeO2-Al2O3 is an excellent support for this process helping to achieve high degrees of CO2 conversions. Interestingly, FeOx and CrOx, which are well-known active components for the forward shift reaction, have opposite effects when used as promoters in the RWGS reaction. The use of iron remarkably boosts the activity, selectivity and stability of the Ni-based catalysts, while adding chromium results detrimental to the overall catalytic performance. In fact, the iron-doped material was tested under extreme conditions (in terms of space velocity) displaying fairly good activity/stability results. This indicates that this sort of catalysts could be potentially used to design compact RWGS reactors for flexible CO2 utilisation units.
This article presents a CFD model of the multiphase flow inside structured packings for amine-based post-combustion carbon capture. In the literature, simulations are performed at three scales due to computational limitations: small-, meso- and large-scale. This work focuses on small- and meso-scale, introducing interface tracking at both. The interfacial tracking is accomplished by using the Volume of Fluid (VoF) method. Small-scale allows studying the reaction kinetics of the absorption process in 2D geometries. Meso-scale has been used in the literature to describe the dry pressure drop of the packing (single-phase simulations). The interface tracking allows obtaining the relationship between the liquid load and both the liquid hold-up and the interface area. Data from the simulations are compared against experimental results found in the literature. The accurate modeling of the interface area, liquid hold-up and reaction kinetics allows utilizing this CFD model as a design tool for novel packings or to optimizing geometries already in use.
A two-dimensional numerical
fluid model is developed for studying the influence of
packing configurations on dielectric barrier discharge (DBD) characteristics. Dis-
charge current profiles, and time averaged electric field strength, electron number
density and electron temperature distributions are compared for the three DBD configurations, plain DBD with no packing, partially packed DBD and fully packed DBD.
The results show a strong change in discharge behaviour occurs when a DBD is fully
packed as compared to partial packing or no packing. While the average electric
field strength and electron temperature of a fully packed DBD are higher relative
to the other DBD configurations, the average electron density is substantially lower
and may impede the DBD reactor performance under certain operating conditions.
Possible scenarios of the synergistic effect of the combination of plasma with catalysis
are also discussed.
CO2 reforming of methane is an effective route for carbon dioxide recycling to valuable syngas. However conventional catalysts based on Ni fail to overcome the stability requisites in terms of resistance to coking and sintering. In this scenario, the use of Sn as promoter of Ni leads to more powerful bimetallic catalysts with enhanced stability which could result in a viable implementation of the reforming technology at commercial scale. This paper uses a combined computational (DFT) and experimental approach, to address the fundamental aspects of mitigation of coke formation on the catalyst?s surface during dry reforming of methane (DRM). The DFT calculation provides fundamental insights into the DRM mechanism over the mono and bimetallic periodic model surfaces. Such information is then used to guide the design of real powder catalysts. The behaviour of the real catalysts mirrors the trends predicted by DFT. Overall the bimetallic catalysts are superior to the monometallic one in terms of long-term stability and carbon tolerance. In particular, low Sn concentration on Ni surface effectively mitigate carbon formation without compromising the CO2 conversion and the syngas production thus leading to excellent DRM catalysts. The bimetallic systems also presents higher selectivity towards syngas as reflected by both DFT and experimental data. However, Sn loading has to be carefully optimized since a relatively high amount of Sn can severely deter the catalytic performance.
As the regulatory limitations of hard-chrome plating surge, the successful application of thermal- sprayed wear/corrosion resistant coatings on complex geometries becomes critical. Thermal spraying is a line-of-sight method and thus, spraying a complex geometry results to changes in the spray angle, the spray distance and the effective gun traverse speed. Although there has been some research on the effects of these kinematic parameters on the coatings, previous work tends to examine the kinematic parameters in isolation, disregarding of any interplay between them. Yet, the effective particle velocity at impingement is dictated both by spray angle and spray distance while the particle temperature is mainly dictated by spray distance. In addition, the heat and mass transfer to the underlying coating are controlled by the gun traverse speed. These facts suggest that significant synergistic effects are expected when the spray kinematic parameters vary simultaneously, as when a complex geometry is sprayed. This work aims at evaluating the systemic effect of the spray kinematic parameters on WC-Co coatings sprayed by HVOF. Various coating properties are comprehensively examined and discussed, exploring the microstructures, phase composition, mechanical qualities and tribological performance. Significant interplay between the spray kinematic parameters is demonstrated in a number of coating properties, yielding non-linear behaviours. The notable beneficial role of small spray angle inclinations at long spray distances, in regards to deposition rate, microstructure, microhardness and wear resistance is demonstrated. Mechanisms of the particle rebounding, superficial oxidation of the coating, metallic tungsten crystallization, tribofilm formation and wear damage progression are proposed, with respect to the spray kinematic parameters. Finally, an attempt to generalize the insights from this work to any given sprayable geometry takes place in a prototype software tool in Matlab.
An optimised integration approach connecting a conventional oil refinery with an ethylene production plant is investigated. Using the intermediate materials produced as the connection between the two plants, the use of internally provided feedstocks and blending options removes, at least partially, the reliance on external sourcing. This is also beneficial in terms of increasing profit margins and quality for both production systems. Thus, a mathematical model has been developed and implemented in this work to model the oil refinery and the ethylene production plant while considering their integration as an MINLP problem with the aim of optimising the integrated plants. This work considers the optimisation of each plant individually and later the final integration by modelling the interconnection between the oil refinery and the ethylene production plant. Moreover, a case study using practical data was carried out to verify the feasibility of the integration for an industrial application.
The vanadium redox flow battery (VRFB) has emerged as a promising technology for large-scale storage of intermittent power generated from renewable energy sources due to its advantages such as scalability, high energy efficiency and low cost. In the current study, a three-dimensional(3D) Lattice Boltzmann model is developed to simulate the transport mechanisms of electrolyte flow, species and charge in the vanadium redox flow battery at the micro pore scale. An electrochemical model using the Butler-Volmer equation is used to provide species and charge coupling at the surface of active electrode. The detailed structure of the carbon paper electrode is obtained using X-ray Computed Tomography(CT). The new model developed in the paper is able to predict the local concentration of different species, over-potential and current density profiles under charge/discharge conditions. The simulated capillary pressure as a function of electrolyte volume fraction for electrolyte wetting process in carbon paper electrode is presented. Different wet surface area of carbon paper electrode correspond to different electrolyte volume fraction in pore space of electrode. The model is then used to investigate the effect of wetting area in carbon paper electrode on the performance of vanadium redox flow battery. It is found that the electrochemical performance of positive half cell is reduced with air bubbles trapped inside the electrode.
The thermal dissolution and decarburization of WC-based powders that occur in various spray processes are a widely studied phenomenon, and mechanisms that describe its development have been proposed. However, the exact formation mechanism of decarburization products such as metallic W is not yet established. A WC-17Co coating is sprayed intentionally at an exceedingly long spray distance to exaggerate the decarburization effects. Progressive xenon plasma ion milling of the examined surface has revealed microstructural features that would have been smeared away by conventional polishing. Serial sectioning provided insights on the three-dimensional structure of the decarburization products. Metallic W has been found to form a shell around small splats that did not deform significantly upon impact, suggesting that its crystallization occurs during the in-flight stage of the particles. W2C crystals are more prominent on WC faces that are in close proximity with splat boundaries indicating an accelerated decarburization in such sites. Porosity can be clearly categorized in imperfect intersplat contact and oxidation-generated gases via its shape.
Catalytic hydrodeoxygenation (HDO) is a fundamental
process for bio-resources upgrading to produce transportation
fuels or added value chemicals. The bottleneck of this technology
to be implemented at commercial scale is its dependence on high
pressure hydrogen, an expensive resource which utilization also
poses safety concerns. In this scenario, the development of
hydrogen-free alternatives to facilitate oxygen removal in biomass
derived compounds is a major challenge for catalysis science but
at the same time it could revolutionize biomass processing
technologies. In this review we have analyzed several novel
approaches, including catalytic transfer hydrogenation (CTH),
combined reforming and hydrodeoxygenation, metal hydrolysis
and subsequent hydrodeoxygenation along with non-thermal
plasma (NTP) in order to avoid the supply of external H2. The
knowledge accumulated from traditional HDO sets the grounds
for catalysts and processes development among the hydrogen
alternatives. In this sense, mechanistic aspects for HDO and the
proposed alternatives are carefully analyzed in this work.
Biomass model compounds are selected aiming to provide an indepth
description of the different processes and stablish solid
correlations catalysts composition-catalytic performance which
can be further extrapolated to more complex biomass feedstocks.
Moreover, the current challenges and research trends of novel
hydrodeoxygenation strategies are also presented aiming to
spark inspiration among the broad community of scientists
working towards a low carbon society where bio-resources will
play a major role.
Mo2C is an effective catalyst for chemical CO2 upgrading via reverse water-gas shift (RWGS). In this work, we demonstrate that the activity and selectivity of this system can be boosted by the addition of promoters such as Cu and Cs. The addition of Cu incorporates extra active sites such as Cu+ and Cu0 which are essential for the reaction. Cs is an underexplored dopant whose marked electropositive character generates electronic perturbations on the catalyst?s surface leading to enhanced catalytic performance. Also, the Cs-doped catalyst seems to be in-situ activated due to a re-carburization phenomenon which results in fairly stable catalysts for continuous operations. Overall, this work showcases a strategy to design highly efficient catalysts based on promoted ²-Mo2C for CO2 recycling via RWGS.
In this work, bimetallic Cu?Ni catalysts have been studied in the water-gas shift (WGS) reaction, and they have shown different levels of synergy and anti-synergy in terms of catalytic activity and selectivity to the desired products. Cu?Ni interactions alter the physicochemical properties of the prepared materials (i.e. surface chemistry, redox behaviour, etc.) and as a result, the catalytic trends are influenced by the catalysts' composition. Our study reveals that Cu enhances Ni selectivity to CO2 and H2 by preventing CO/CO2 methanation, while Ni does not help to improve Cu catalytic performance by any means. Indeed, the monometallic Cu formulation has shown the best results in this study, yielding high levels of reactants conversion and excellent long-term stability. Interestingly, for medium-high temperatures, the bimetallic 1Cu?1Ni outperforms the stability levels reached with the monometallic formulation and becomes an interesting choice even when start-up/shutdowns operations are considered during the catalytic experiments.
Gas turbines are of great importance in industry. In the turbine section within a jet engine, thermal barrier coatings (TBCs) are utilized to protect the metal turbine blades, thus improve the efficiency of engine. However, this coating is extremely vulnerable to attack by injected particulates. This ingested particulate is often referred to as "CMAS" (Calcia-Magnesia-Alumina-Silica). Among all the CMAS materials, Volcanic Ash (VA) is the most common type which aeroengines may encounter during the flight. This type of CMAS material would melt in the combustion section by ultra high temperature and then impact the turbine blades with relatively high speed. Some of the particles would then stick on and bond with the TBC, thus cause degradation of the protecting coating. In this way, the jet engine would be permanently damaged.
In the recent years, experiments have been done by different researchers to elaborate the effect of CMAS materials on TBCs. However, there is still a lack of knowledge in the bonding mechanism and physical adhesion between the CMAS particles (especially VA particles) and the substrate. A study of VA particle impingement is required in order to understand particle impingement, phase transition and heat transfer, bonding mechanism and splat morphology in detail.
In this research, experiments were carried at Cambridge University, by Prof. Trevor William Clyne, Dr. James Dean and Dr. Catalina Taltavull to reproduce the VA-substrate impingement in jet engine. A Vacuum Plasma Spray (VPS) system was utilized to create a high-temperature, high-velocity flow field. Different types of Volcanic Ashes (VAs) were introduced into the experimental set-up. Sticking rate, Scanning Electron microscope (SEM) micrographs of deposition morphology were examined and collected. Chapter 3 elaborates the details of this experiment set-up and data collected from the experiment. This experiment set-up is utilized by the author for building numerical models and the result of this experiment is used to validate the numerical models.
Three numerical models were built to perform a systematic study. Firstly, in Chapter 4, a Computational Fluid Dynamic (CFD) model was created to simulate the steady-state of the VPS flow field. The Discrete Particle Method (DPM) model was then utilized to simulate the injection of volcanic ash particles. After calculating the BI number, non-isothermal effects within the ceramic particles were simulated by introducing the heat transfer function by a user-defined function (UDF). This model gives the temperature gradient within and velocity of the in-flight VA particles at any time during the spray. It is shown that small particles (diameter $50\ \mu m$) would easily impact the turbine blades, but would remain unmelted due to the large grain size. It is concluded that VA particles with diameter of $15\ \mu m$ to $40\ \mu m$ are the most "dangerous" particles, because these particles have both relatively high possibility to be melted, and high possibility to impact thus adhere on the substrate.
Second of all in Chapter 5, systematic study of Yttria-stabilized Zirconia (YSZ) particle impingement and deposition on stainless steel in thermal spray process has been performed. A Coupled Eulerian and Lagrangian model was developed. This model contributes to simulate the process of semi-molten particle impact. By utilizing this model, both the large deformation of liquid part and the plastic deformation of the solid part could be extracted. One fully molten and two semi-molten(solid core with liquid shell and solid shell with liquid core) cases were studied. The results of the numerical model matches well with the experiment and analytical data. Interest parameters such as velocity, temperature, fraction of liquid p
In this letter, a non-orthogonal multiple access (NOMA) scheme is employed for irregular repetition slotted ALOHA (IRSA). Specifically, packet replicas are transmitted with discrete power levels which are pre-determined by the NOMA scheme. In this case, most packet collisions can be resolved in the power domain, contributing to a much lower packet loss rate. Density evolution (DE) analysis is formulated and the degree distributions are optimized for different number of power levels. Simulation results validate our analysis and show that the proposed scheme can outperform existing IRSA schemes.
It has become increasingly important to control carbon dioxide (CO¬2) emissions and at the same time generate fuel sources to meet the growing global energy consumption need. CO2 (dry) reforming of methane (DRM) is a viable process as it generates fuel (syngas) and utilises greenhouse (CH4 and CO2) gas at the same time. The success of this process relies on the development of suitable noble-metal free catalysts. First principle?s based computational methods, such as density functional theory (DFT), has become a powerful predictive tool for catalyst development in modern science. Therefore the main objective of this thesis work has been to investigate suitable catalysts using computational methods for gas?phase CO2 utilisation reactions.
In this research work, DFT calculations provided us with the fundamental insights into the DRM mechanism over bimetallic Sn/ Ni (111) periodic model surfaces. This analysis showed that low Sn concentration on Ni surface effectively mitigates carbon formation without compromising the CO2 conversion and the syngas production, showcasing superior characteristics of the bimetallic catalyst towards carbon tolerance stability. Other heterogeneous catalysts such as Ni2P and MoP have also been studied in this thesis. Theoretical analysis of DRM reaction on the unexplored nickel phosphide Ni2P (0001) surface showcased suitable syngas production under DRM reaction temperatures with low carbon deposition formation on the surface. This was mainly attributed to a lower number of active sites available for carbon adsorption compared to oxygen on the Ni2P (0001) surface.
DFT study on activation of CO2 and CO on MoP (0001) and Ni2P (0001) surfaces showcased selective CO production from CO2 to be possible on both the surfaces. Further, direct CO activation is favoured on the MoP (0001) surface. Surface bounded oxygen removal on Ni2P (0001) is reasonably favourable.
Findings from this thesis work will be beneficial in developing more robust catalysts for gas phase CO2 utilisation reactions and could contribute to a better understanding of CO2 conversion processes, catalysts deactivation and thus helping to develop new families of powerful catalysts for a greener society
This study reports the potential application of Ni2P as highly effective catalyst for chemical CO2 recycling via dry reforming of methane (DRM). Our DFT calculations reveal that the Ni2P (0001) surface is active towards adsorption of the DRM species, with the Ni hollow site being the most energetically stable site and Ni-P and P contributes as co-adsorption sites in DRM reaction steps. Free energy analysis at 1000 K found CH-O to be the main pathway for CO formation. The competition of DRM and reverse water gas shift (RWGS) is also evidenced with the latter becoming important at relatively low reforming temperatures. Very interestingly oxygen seems to play a key role in making this surface resistant towards coking. From microkinetic analysis we have found greater oxygen surface coverage than that of carbon at high temperatures which may help to oxidize carbon deposits in continuous runs. The tolerance of Ni2P towards carbon deposition was further corroborated by DFT and micro kinetic analysis. Along with the higher probability of C oxidation we identify poor capacity of carbon diffusion on the Ni2P (0001) surface with very limited availability of C nucleation sites. Overall, this study opens new avenues for research in metal-phosphide catalysis and expands the application of these materials to CO2 conversion reactions.